EP0473105B1 - Herstellung von Pentafluordichlorpropanen - Google Patents

Herstellung von Pentafluordichlorpropanen Download PDF

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Publication number
EP0473105B1
EP0473105B1 EP91114338A EP91114338A EP0473105B1 EP 0473105 B1 EP0473105 B1 EP 0473105B1 EP 91114338 A EP91114338 A EP 91114338A EP 91114338 A EP91114338 A EP 91114338A EP 0473105 B1 EP0473105 B1 EP 0473105B1
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Prior art keywords
anhydrous
chloroform
catalyst
reaction
mixture
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French (fr)
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EP0473105A1 (de
Inventor
Hirokazu C/O Yodogawa Works Of Aoyama
Satoru C/O Yodogawa Works Of Kono
Takashi C/O Yodogawa Works Of Yasuhara
Souichi C/O Yodogawa Works Of Ueda
Satoshi C/O Yodogawa Works Of Koyama
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority claimed from JP2227501A external-priority patent/JPH0784398B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons

Definitions

  • the present invention relates to a process for preparing pentafluorodichloropropanes, in particular, 1,1,1,2,2-pentafluoro-3,3-dichloropropane (hereinafter referred to as "R-225ca”) and 1,1,2,2,3-pentafluoro-1,3-dichloropropane (hereinafter referred to as "R-225cb”) which are substitute compounds for industrially important 1,1,2-trichloro-1,2,2-trifluoroethane and have less influence on the global environment.
  • R-225ca 1,1,1,2,2-pentafluoro-3,3-dichloropropane
  • R-225cb 1,1,2,2,3-pentafluoro-1,3-dichloropropane
  • the present invention also relates to removal of chloroform from R-225ca and/or R-225cb.
  • R-225ca and R-225 cb are prepared, for example, by batchwise reacting tetrafluoroethylene (hereinafter referred to as "TFE”) with dichlorofluoromethane (hereinafter referred to as "R-21”) in the presence of a catalyst such as anhydrous aluminum chloride at a temperature of 15 to 100°C in an autoclave or a glass reactor (cf. U.S. Patent No. 2,462,402, J. Am. Chem. Soc., 71 , 979 (1949) and Col. Czech. Chem. Com., 36 (1867)).
  • TFE tetrafluoroethylene
  • R-21 dichlorofluoromethane
  • R-225ca can be prepared by reacting TFE with cesium fluoride in diglyme and further with chloroform (cf. U.S. Patent No. 3,381,042).
  • the products should be separated from the catalyst by collecting the products in a cold trap under reduced pressure or by treating the catalyst with hydrochloric acid and separating the products.
  • chloroform forms an azeotropic mixture with each of R-225ca and R-225cb, a large amount of R-225ca and R-225cb are lost when chloroform is removed from the mixture by rectification to obtain pure R-225ca or R-225cb.
  • One object of the present invention is to provide a novel process for preparing R-225ca and R-225cb in a high selectivity and yield.
  • Another object of the present invention is to provide a process for removing chloroform from R-225ca and/or R-225cb.
  • a process for preparing R-225ca and R-225cb which comprises reacting chloroform, difluorochloromethane and TFE in the presence of a catalyst.
  • a process for removing chloroform from a mixture of chloroform and at least one pentafluorodichloropropane selected from the group consisting of R-225ca and R-225cb which comprises reacting difluorochloromethane and TFE with chloroform in said mixture in the presence of a catalyst.
  • the catalyst may be any one of catalysts which are catalytically active for an addition reaction of R-21 to TFE.
  • a Lewis acid is preferred.
  • the catalyst are anhydrous aluminum chloride, anhydrous titanium tetrachloride, anhydrous tin tetrachloride, anhydrous antimony pentachloride, anhydrous zinc chloride, anhydrous iron chloride, anhydrous aluminum bromide, boron trifluoride, etc.
  • a compound of the formula: AlCl x F y O z (I) wherein x, y and z are numbers which satisfy the equations: x + y + 2z 3, 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 3 and 0 ⁇ z ⁇ 3/2 provided that at least one of y and z is not zero, such as aluminum chloride fluoride and alumina chloride fluoride can be used.
  • Aluminum chloride fluoride to be used as a catalyst in the present invention can be prepared by reacting aluminum chloride with hydrogen fluoride, hydrofluoric acid, or a fluoro- or chlorofluoro-hydrocarbon having not more than 4 carbon atoms, preferably not more than 2 carbon atoms (e.g. trifluoromethane, tetrafluoroethane, chlorodifluoromethane, dichlorofluoromethane, trifluorodichloroethane, trifluorochloromethane, difluorotetrachloroethane, trifluorotrichloroethane, etc.). They may be used alone or in combination. Alternatively, they may be used in combination with a chlorohydrocarbon.
  • a reaction temperature is from 0 to 120°C, preferably from 0 to 100°C. The reaction may be carried out in a liquid phase or a vapor phase.
  • Alumina chloride fluoride to be used as a catalyst in the present invention can be prepared by reacting activated alumina with a chloro-, chlorofluoro- or fluorohydrocarbon, hydrogen chloride or their mixture at a temperature of 100 to 700°C.
  • alumina is filled in a reactor tube made of stainless steel, Hasteloy or glass and heated to a temperature of 300 to 500°C in a stream of dried nitrogen to thoroughly dry alumina. Then, at the above specified temperature, preferably from 100 to 600°C, more preferably from 200 to 400°C, the above halogenated hydrocarbon alone or its mixture with hydrogen chloride or oxygen is passed through the reactor tube.
  • alumina chloride fluoride may be prepared by treating activated alumina with hydrogen chloride gas.
  • activated alumina is heated at a temperature of 400 to 800°C to thoroughly dry alumina.
  • hydrogen chloride as such or diluted with an inert gas (e.g. nitrogen, argon, etc.) or a chlorofluorohydrocarbon (e.g. R-12 (dichlorodifluoromethane), R-21, etc.) is passed over dried alumina.
  • the passing time is usually from 3 to 10 hours.
  • any commercially available porous alumina which comprises ⁇ -alumina and is used for dehydration or as a catalyst can be used.
  • examples of such alumina are Neobead C, MH, GB and D (all manufactured by Mizusawa Chemical Industries, Ltd.) and activated alumina KHA, NKH 1 and NKH 3 (all manufactured by Sumitomo Chemical Company, Ltd.)
  • chloro- or chlorofluoro-hydrocarbon having no hydrogen those having 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms are used.
  • Preferred examples are carbon tetrachloride, fluorotrichloromethane, difluorodichloromethane, trifluorochloromethane, 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,1-trichloro-2,2,2-trifluoroethane, 1,1,2,2-tetrafluoro-1,2-dichloroethane, 1,1,1,2-tetrafluoro-2,2-dichloroethane, 1,1,2,2-tetrachloro-1,2-difluoroethane, 1,1,1,2-tetrachloro-2,2-difluoroethane, etc.
  • chloro- or chlorofluoro-hydrocarbon having a hydrogen atom those having 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms are used.
  • Preferred examples are fluorodichloromethane, difluorochloromethane, 1,1,1-trifluoro-2,2-dichloroethane, 1,1,2-trifluoro-1,2-dichloroethane, 1,1,1-trifluoro-2-chloroethane, etc.
  • the alumina chloride fluoride catalyst can be prepared by reacting alumina with an inorganic fluoride such as hydrogen fluoride at a temperature of 20 to 450°C; sulfur fluoride (e.g. SF4, SF6, etc.), sulfuryl fluoride or thionyl fluoride at a temperature of 300 to 500°C; or an ammonium fluoride (e.g. acidic ammonium fluoride, neutral ammonium fluoride, etc.) at a temperature of 20 to 450°C, and then treating a product with a chlorofluoro- or chloro-hydrocarbon or hydrogen chloride.
  • an inorganic fluoride such as hydrogen fluoride at a temperature of 20 to 450°C
  • sulfur fluoride e.g. SF4, SF6, etc.
  • sulfuryl fluoride or thionyl fluoride at a temperature of 300 to 500°C
  • an ammonium fluoride e.g. acidic ammonium fluor
  • the catalysts may be used as a mixture of two or more of them.
  • catalysts to be used in the present invention particularly preferred catalyst are anhydrous aluminum chloride and the catalyst of the above formula (I).
  • the most preferred reaction mode is a continuous reaction mode in which the raw materials are continuously fed and the product is continuously removed, though it is possible to use a semi-batchwise process in which certain amounts of the raw materials are continuously fed and stopped, the reaction is carried out for a certain time and then the reaction product is recovered.
  • chloroform, R-22 and TFE may be reacted in a solvent.
  • solvents which are inactive to the catalyst and in which chloroform, R-22 and TFE are dissolved can be used.
  • chloroform may be used as the solvent.
  • Tetrafluorotrichloropropanes which are by-produced hydrochlorofluoroalkanes may be used as the solvents.
  • a conventional solvent such as chloroalkanes (e.g. dichloromethane) or chlorofluoroalkanes (e.g. tetrachlorotetrafluoropropanes) may be used as the solvent.
  • chloroform which is one of the raw materials is preferred.
  • R-225 as such is preferred.
  • R-225ca, R-225cb or their mixture When anhydrous aluminum chloride is used as the catalyst and R-225ca, R-225cb or their mixture is used as the solvent, a specific amount of anhydrous aluminum chloride is suspended in the solvent, and then chloroform, R-22 and TFE are charged in the suspension at a specific molar ratio at specific flow rates.
  • a reaction mixture containing formed R-225ca and R-225cb is separated from suspended anhydrous aluminum chloride and recovered from the reactor.
  • the reaction mixture can be separated from suspended anhydrous aluminum chloride by a conventional method, for example, filtration in a liquid state or distillation in a vapor state.
  • the separated reaction mixture is further purified by a conventional method such as rectification to obtain R-225ca and R-225cb.
  • a weight ratio of the solvent to the catalyst is at least two. When this ratio is smaller than 2, the reaction system cannot be effectively stirred so that, in an initial stage, the selectivity of R-225ca and R-225cb tends to decrease.
  • a molar ratio among chloroform, R-22 and TFE will be explained.
  • a molar ratio of chloroform to R-22 is at least 1:1, preferably from 1:1 to 1:10, and a molar ratio of R-22 to TFE is at least 1:2, preferably from 1:2 to 1:10.
  • a molar ratio of chloroform:R-22:TFE is, for example, 1:2:4.
  • Chloroform, R-22 and TFE may be premixed and then charged in the reactor, or they may be charged simultaneously without premixing. In some cases, a certain amount of chloroform is charged for a certain time and then a mixture of R-22 and TFE is charged.
  • Each of the raw materials may be used in a gas form or a liquid form.
  • a reaction pressure is not critical and may be reduced pressure. However, in view of simplicity of the reactor, atmospheric pressure or higher is preferred.
  • a reaction temperature is usually from -30 to +120°C, preferably from -20 to +60°C.
  • the reaction temperature is higher than 120°C, amounts of by-products increase and the selectivity of R-225ca and R-225cb decreases.
  • the reaction temperature is lower than -30°C, the reaction rate becomes unpractically low.
  • the raw materials namely chloroform, R-22 and TFE are industrially produced and commercially available.
  • the Lewis acid such as anhydrous aluminum is a commercially available compound and used in the present invention without treatment.
  • the catalyst is suspended in the mixture of R-225ca, R-225cb and chloroform, and then TFE and R-22 are charged at the specific ratio at the specific temperature. Progress of the reaction is monitored by gas chromatography and the reaction is terminated when chloroform is not detected.
  • the suspended catalyst is separated from the mixture to recover desired R-225ca and R-225cb.
  • the separation of the catalyst can be carried in the same way as above.
  • TFE and R-22 in the gas state are continuously bubbled though the reaction mixture under atmospheric pressure, or the reaction mixture is charged in an autoclave and then TFE and R-22 are charged in the autoclave under pressure to carry out the reaction.
  • a reaction pressure is not critical.
  • a molar ratio of TFE to R-22 is not limited. At least one mole of TFE is used per one mole of R-22. A large excessive amount of TFE does not have any influence on the reaction. However, unreacted TFE may escape from the reaction mixture and a large amount of TFE is lost. In view of economy, an upper limit of TFE is 3 moles per one mole of R-22.
  • a reaction temperature may be the same as above.
  • Anhydrous aluminum chloride fluoride was prepared as follows: Anhydrous aluminum chloride (20 g) and fluorotrichloromethane (20 g) were mixed and stirred at a temperature of 0 to 5°C for 2 hours. Then, the reaction mixture was evaporated under reduced pressure to obtain anhydrous aluminum chloride fluoride.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (8)

  1. Verfahren zur Herstellung von 1,1,1,2,2,-Pentafluor-3,3-dichlorpropan und 1,1,2,2,3,-Pentafluor-1,3-dichlorpropan, umfassend das Umsetzen von Chloroform, Difluorchlormethan und Tetrafluorethylen in Gegenwart eines Katalysators.
  2. Verfahren gemäß Anspruch 1, bei dem der Katalysator eine Lewissäure ist.
  3. Verfahren gemäß Anspruch 1, bei dem der Katalysator wenigstens einer ausgewählt aus der Gruppe, bestehend aus wasserfreiem Aluminiumchlorid, wasserfreiem Titantetrachlorid, wasserfreiem Zinntetrachlorid, wasserfreiem Antimonpentachlorid, wasserfreiem Zinkchlorid, wasserfreiem Eisenchlorid, wasserfreiem Aluminiumbromid, Bortrifluorid und einer Verbindung der Formel:



            AlClxFyO₂   (I)



    worin x, y und z Zahlen sind, welche den Gleichungen entsprechen:

    x + y + 2z = 3,
    Figure imgb0013
    0 < x < 3,
    Figure imgb0014
    0 ≦ y < 3 und
    Figure imgb0015
    0 ≦ z < 3/2
    Figure imgb0016

    unter der Voraussetzung, daß wenigstens eines von y und z nicht 0 ist, ist.
  4. Verfahren gemäß Anspruch 1, bei dem die Umsetzung in Abwesentheit eines zusätzlichen Lösungsmittels durchgeführt wird.
  5. Verfahren gemäß Anspruch 1, bei dem die Umsetzungstemperatur von -30 bis +120°C ist.
  6. Verfahren zum Entfernen von Chloroform aus einer Mischung von Chloroform und wenigstens einem Pentafluordichlorpropan ausgewählt aus der Gruppe, bestehend aus 1,1,1,2,2,-Pentafluor-3,3-dichlorpropan und 1,1,2,2,3,-Pentafluor-1,3-dichlorpropan, umfassend das Umsetzen von Difluorchlormethan und Tetrafluorethylen mit Chloroform in der Mischung in Gegenwart eines Katalysators.
  7. Verfahren gemäß Anspruch 6, bei dem der Katalysator eine Lewissäure ist.
  8. Verfahren gemäß Anspruch 6, bei dem der Katalysator wenigstens einer ausgewählt aus der Gruppe, bestehend aus wasserfreiem Aluminiumchlorid, wasserfreiem Titantetrachlorid, wasserfreiem Zinntetrachlorid, wasserfreiem Antimonpentachlorid, wasserfreiem Zinkchlorid, wasserfreiem Eisenchlorid, wasserfreiem Aluminiumbromid, Bortrifluorid und einer Verbindung der Formel:



            AlClxFyO₂   (I)



    worin x, y und z Zahlen sind, welche den Gleichungen entsprechen:

    x + y + 2z = 3,
    Figure imgb0017
    0 < x < 3,
    Figure imgb0018
    0 ≦ y < 3 und
    Figure imgb0019
    0 ≦ z < 3/2
    Figure imgb0020

    unter der Voraussetzung, daß wenigstens eines von y und z nicht 0 ist, ist.
EP91114338A 1990-08-28 1991-08-27 Herstellung von Pentafluordichlorpropanen Expired - Lifetime EP0473105B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP227502/90 1990-08-28
JP2227502A JPH0784399B2 (ja) 1990-08-28 1990-08-28 ペンタフルオロジクロロプロパン中のクロロホルムの除去方法
JP227501/90 1990-08-28
JP2227501A JPH0784398B2 (ja) 1990-08-28 1990-08-28 ペンタフルオロジクロロプロパン類の製造方法

Publications (2)

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EP0473105A1 EP0473105A1 (de) 1992-03-04
EP0473105B1 true EP0473105B1 (de) 1995-03-01

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EP (1) EP0473105B1 (de)
KR (1) KR920004321A (de)
AT (1) ATE119143T1 (de)
BR (1) BR9103700A (de)
CA (1) CA2049821A1 (de)
CS (1) CS263391A3 (de)
DE (1) DE69107732T2 (de)
DK (1) DK0473105T3 (de)
ES (1) ES2071878T3 (de)
PL (1) PL291537A1 (de)
RU (1) RU2029757C1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0525066A (ja) * 1991-07-23 1993-02-02 Daikin Ind Ltd １，１，１，２，２−ペンタフルオロ−３，３−ジクロロプロパン及び１，１，２，２，３−ペンタフルオロ−１，３−ジクロロプロパンの製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2462402A (en) * 1945-06-30 1949-02-22 Du Pont Fluorinated hydrocarbons
BE638397A (de) * 1962-10-09
US3381042A (en) * 1967-01-27 1968-04-30 Squibb & Sons Inc Process for preparing halogenated propanes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 43, no. 11, 10 June 1949, pages 979, 980 column 4213, Columbus, Ohio, USA; D. D. Coffman et al, "Synthesis of chlorofluoropropanes". *

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RU2029757C1 (ru) 1995-02-27
KR920004321A (ko) 1992-03-27
DE69107732D1 (de) 1995-04-06
BR9103700A (pt) 1992-05-19
PL291537A1 (en) 1992-04-06
EP0473105A1 (de) 1992-03-04
CA2049821A1 (en) 1992-03-01
CS263391A3 (en) 1992-04-15
DK0473105T3 (da) 1995-05-22
DE69107732T2 (de) 1995-08-24
ES2071878T3 (es) 1995-07-01
ATE119143T1 (de) 1995-03-15

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